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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Ozone Gas: Scientific Justification and Practical Guidelines for Improvised Disinfection using Consumer-Grade Ozone Generators and Plastic Storage Boxes

Here, we describe direct measurements of ozone concentration achievable in small enclosed containers (plastic storage boxes) for use as improvised decontamination systems for small articles such as disposable PPE (N95 masks, nitrile gloves, etc.), clothing, mail and small packages, food, and other miscellaneous articles. The emphasis is on the reliable and sustained generation of ozone gas concentrations of sufficient concentration and duration to create an effective virucidal environment to achieve more than 95% to 99% viral inactivation, based upon the data already published in the peer-review literature on this topic. The suggestion that ozone be used to inactivate virus is certainly not a new idea. Our objective in this report is to make clear that the necessary levels of ozone can be improvised using simple, easy-to-use, inexpensive, and widely available supplies, and that there is every theoretical and experimental reason to believe that this approach is as highly effective in viral inactivation by ozone as are the far more expensive, complex, cumbersome, and less available equivalent ozone (and other) disinfectant systems that have themselves become unavailable during times of pandemic crisis. Using multiple types of readily available commercial ozone generators, concentration in the tested improvised enclosure is tracked over time to assess ozone charging and decay rates, and the ozone quenching effects of items placed in the box. Generator performance is compared against published ozone dosage values for virucidal and antimicrobial activity. Bubbler and box-fan-type ozone generators were found to be effective at achieving and maintaining target concentrations of 10ppm ozone or higher, whereas automotive cigarette lighter and universal serial bus type plug in “air freshener” ozone generators could not achieve the target concentrations in these experiments. Calculations and practical guidelines for assembly and effective use of an ozone box for improvised decontamination are offered. The majority of this report is directed toward the scientific justification and rationale for this approach. The end of the document summarizes the findings and offers simplified designs for the construction and use of ozone boxes as an improvised method of disinfection.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2014

Not just about sunburn – the ozone hole's profound effect on climate has significant implications for Southern Hemisphere ecosystems

Abstract Climate scientists have concluded that stratospheric ozone depletion has been a major driver of Southern Hemisphere climate processes since about 1980. The implications of these observed and modelled changes in climate are likely to be far more pervasive for both terrestrial and marine ecosystems than the increase in ultraviolet‐B radiation due to ozone depletion; however, they have been largely overlooked in the biological literature. Here, we synthesize the current understanding of how ozone depletion has impacted Southern Hemisphere climate and highlight the relatively few documented impacts on terrestrial and marine ecosystems. Reviewing the climate literature, we present examples of how ozone depletion changes atmospheric and oceanic circulation, with an emphasis on how these alterations in the physical climate system affect Southern Hemisphere weather, especially over the summer season (December–February). These potentially include increased incidence of extreme events, resulting in costly floods, drought, wildfires and serious environmental damage. The ecosystem impacts documented so far include changes to growth rates of South American and New Zealand trees, decreased growth of Antarctic mosses and changing biodiversity in Antarctic lakes. The objective of this synthesis was to stimulate the ecological community to look beyond ultraviolet‐B radiation when considering the impacts of ozone depletion. Such widespread changes in Southern Hemisphere climate are likely to have had as much or more impact on natural ecosystems and food production over the past few decades, than the increased ultraviolet radiation due to ozone depletion.

Robinson, Sharon A.↗
DOE OSTI2017

Tropospheric Ozone Assessment Report: Database and Metrics Data of Global Surface Ozone Observations

In support of the first Tropospheric Ozone Assessment Report (TOAR) a relational database of global surface ozone observations has been developed and populated with hourly measurement data and enhanced metadata. A comprehensive suite of ozone data products including standard statistics, health and vegetation impact metrics, and trend information, are made available through a common data portal and a web interface. These data form the basis of the TOAR analyses focusing on human health, vegetation, and climate relevant ozone issues, which are part of this special feature. Cooperation among many data centers and individual researchers worldwide made it possible to build the world's largest collection of in-situ hourly surface ozone data covering the period from 1970 to 2015. By combining the data from almost 10,000 measurement sites around the world with global metadata information, new analyses of surface ozone have become possible, such as the first globally consistent characterisations of measurement sites as either urban or rural/remote. Exploitation of these global metadata allows for new insights into the global distribution, and seasonal and long-term changes of tropospheric ozone and they enable TOAR to perform the first, globally consistent analysis of present-day ozone concentrations and recent ozone changes with relevance to health, agriculture, and climate. Considerable effort was made to harmonize and synthesize data formats and metadata information from various networks and individual data submissions. Extensive quality control was applied to identify questionable and erroneous data, including changes in apparent instrument offsets or calibrations. Such data were excluded from TOAR data products. Limitations of a posteriori data quality assurance are discussed. As a result of the work presented here, global coverage of surface ozone data for scientific analysis has been significantly extended. Yet, large gaps remain in the surface observation network both in terms of regions without monitoring, and in terms of regions that have monitoring programs but no public access to the data archive. Therefore future improvements to the database will require not only improved data harmonization, but also expanded data sharing and increased monitoring in data-sparse regions.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2015

Valuing the Ozone-Related Health Benefits of Methane Emission Controls

Methane is a greenhouse gas that oxidizes to form ground-level ozone, itself a greenhouse gas and a health-harmful air pollutant. Reducing methane emissions will both slow anthropogenic climate change and reduce ozone-related mortality. We estimate the benefits of reducing methane emissions anywhere in the world for ozone-related premature mortality globally and for eight geographic regions. Our methods are consistent with those used by the U.S. Government to estimate the Social Cost of Carbon (SCC). We find that the global short- and long-term premature mortality benefits due to reduced ozone production from methane mitigation are (2011)$790 and $1775 per tonne methane, respectively. These correspond to approximately 70% and 150% of the valuation of methane’s global climate impacts using the SCC after extrapolating from carbon dioxide to methane using Global Warming Potential (GWP) estimates. Results are most sensitive to the choice of VSL and increase for emission years further in the future. Regionally, most of the global mortality benefits accrue in Asia, but 10% accrue in the United States. This methodology can be used to assess the benefits of methane emission reductions anywhere in the world, including those achieved by national and multinational policies.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2019

Direct observation of C 60 - nano-ion gas phase ozonation via ion mobility-mass spectrometry

Improved methods to probe the reactivity of nano-ions, such as C 60 -, would find utility in nanochemistry, combustion chemistry, and in generally understanding the behavior of matter at the nanometer scale. Here, we demonstrate that ion mobility-mass spectrometry (IM-MS) with a low-field differential mobility analyzer can be used to probe nano-ion reaction kinetics. We used the developed IM-MS approach to examine the gas phase reactivity of C 60 - ions with ozone at atmospheric pressure. Experimental results show that ozonation of C 60 - mainly leads to the formation of C 60 O n -. The controlled reaction time within the ion mobility instrument enables calculation of ozonation reaction rates and assuming oxygen atoms are added sequentially, we find that the reaction rate between C 60 - and O 3 is near the collision controlled limit. We propose an exponentially decaying reaction rate coefficient expression to describe ozonation leading to the addition of >20 oxygen atoms. At high ozone concentrations, CO or CO 2 loss from C 60 O n - is additionally observed.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2016

The transition from the open minimum to the ring minimum on the ground state and on the lowest excited state of like symmetry in ozone: A configuration interaction study

The metastable ring structure of the ozone 1{sup 1}A{sub 1} ground state, which theoretical calculations have shown to exist, has so far eluded experimental detection. An accurate prediction for the energy difference between this isomer and the lower open structure is therefore of interest, as is a prediction for the isomerization barrier between them, which results from interactions between the lowest two {sup 1}A{sub 1} states. In the present work, valence correlated energies of the 1{sup 1}A{sub 1} state and the 2{sup 1}A{sub 1} state were calculated at the 1{sup 1}A{sub 1} open minimum, the 1{sup 1}A{sub 1} ring minimum, the transition state between these two minima, the minimum of the 2{sup 1}A{sub 1} state, and the conical intersection between the two states. The geometries were determined at the full-valence multi-configuration self-consistent-field level. Configuration interaction (CI) expansions up to quadruple excitations were calculated with triple-zeta atomic basis sets. The CI expansions based on eight different reference configuration spaces were explored. To obtain some of the quadruple excitation energies, the method of Correlation Energy Extrapolation by Intrinsic Scaling was generalized to the simultaneous extrapolation for two states. This extrapolation method was shown to be very accurate. On the other hand, none of the CI expansions were found to have converged to millihartree (mh) accuracy at the quadruple excitation level. The data suggest that convergence to mh accuracy is probably attained at the sextuple excitation level. On the 1{sup 1}A{sub 1} state, the present calculations yield the estimates of (ring minimum—open minimum) ∼45–50 mh and (transition state—open minimum) ∼85–90 mh. For the (2{sup 1}A{sub 1}–{sup 1}A{sub 1}) excitation energy, the estimate of ∼130–170 mh is found at the open minimum and 270–310 mh at the ring minimum. At the transition state, the difference (2{sup 1}A{sub 1}–{sup 1}A{sub 1}) is found to be between 1 and 10 mh. The geometry of the transition state on the 1{sup 1}A{sub 1} surface and that of the minimum on the 2{sup 1}A{sub 1} surface nearly coincide. More accurate predictions of the energy differences also require CI expansions to at least sextuple excitations with respect to the valence space. For every wave function considered, the omission of the correlations of the 2s oxygen orbitals, which is a widely used approximation, was found to cause errors of about ±10 mh with respect to the energy differences.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Low ozone dry deposition rates to sea ice during the MOSAiC field campaign: Implications for the Arctic boundary layer ozone budget

Dry deposition to the surface is one of the main removal pathways of tropospheric ozone (O 3 ). We quantified for the first time the impact of O 3 deposition to the Arctic sea ice on the planetary boundary layer (PBL) O 3 concentration and budget using year-round flux and concentration observations from the Multidisciplinary drifting Observatory for the Study of Arctic Climate (MOSAiC) campaign and simulations with a single-column atmospheric chemistry and meteorological model (SCM). Based on eddy-covariance O 3 surface flux observations, we find a median surface resistance on the order of 20,000 s m –1 , resulting in a dry deposition velocity of approximately 0.005 cm s –1 . This surface resistance is up to an order of magnitude larger than traditionally used values in many atmospheric chemistry and transport models. The SCM is able to accurately represent the yearly cycle, with maxima above 40 ppb in the winter and minima around 15 ppb at the end of summer. However, the observed springtime ozone depletion events are not captured by the SCM. In winter, the modelled PBL O 3 budget is governed by dry deposition at the surface mostly compensated by downward turbulent transport of O 3 towards the surface. Advection, which is accounted for implicitly by nudging to reanalysis data, poses a substantial, mostly negative, contribution to the simulated PBL O 3 budget in summer. During episodes with low wind speed (<5 m s –1 ) and shallow PBL (<50 m), the 7-day mean dry deposition removal rate can reach up to 1.0 ppb h –1 . Our study highlights the importance of an accurate description of dry deposition to Arctic sea ice in models to quantify the current and future O 3 sink in the Arctic, impacting the tropospheric O 3 budget, which has been modified in the last century largely due to anthropogenic activities.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2015

Atomic layer deposition of tin oxide and zinc tin oxide using tetraethyltin and ozone

Silicon or glass substrates exposed to sequential pulses of tetraethyltin (TET) and ozone (O{sub 3}) were coated with thin films of SnO{sub 2}. Self-limiting deposition was found using 8 s pulse times, and a uniform thickness per cycle (TPC) of 0.2 nm/cycle was observed in a small, yet reproducible, temperature window from 290 to 320 °C. The as-deposited, stoichiometric SnO{sub 2} films were amorphous and transparent above 400 nm. Interspersing pulses of diethylzinc and O{sub 3} among the TET:O{sub 3} pulses resulted in deposition of zinc tin oxide films, where the fraction of tin, defined as [at. % Sn/(at. % Sn + at. % Zn)], was controlled by the ratio of TET pulses, specifically n{sub TET}:(n{sub TET} + n{sub DEZ}) where n{sub TET} and n{sub DEZ} are the number of precursor/O{sub 3} subcycles within each atomic layer deposition (ALD) supercycle. Based on film thickness and composition measurements, the TET pulse time required to reach saturation in the TPC of SnO{sub 2} on ZnO surfaces was increased to >30 s. Under these conditions, film stoichiometry as a function of the TET pulse ratio was consistent with the model devised by Elliott and Nilsen. The as-deposited zinc tin oxide (ZTO) films were amorphous and remained so even after annealing at 450 °C in air for 1 h. The optical bandgap of the transparent ZTO films increased as the tin concentration increased. Hall measurements established that the n-type ZTO carrier concentration was 3 × 10{sup 17} and 4 × 10{sup 18} cm{sup −3} for fractional tin concentrations of 0.28 and 0.63, respectively. The carrier mobility decreased as the concentration of tin increased. A broken gap pn junction was fabricated using ALD-deposited ZTO and a sputtered layer of cuprous oxide. The junction demonstrated ohmic behavior and low resistance consistent with similar junctions prepared using sputter-deposited ZTO.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2020

Ozone Monitor (OZONE) Instrument Handbook

The primary measurement output from the Thermo Scientific Ozone Analyzer is the concentration of the analyte (O3) reported at 1-s resolution in units of ppbv in ambient air. Note that because of internal pneumatic switching limitations the instrument only makes an independent measurement every 4 seconds. Thus, the same concentration number is repeated roughly 4 times at the uniform, monotonic 1-s time base used in the AOS systems. Accompanying instrument outputs include sample temperatures, flows, chamber pressure, lamp intensities and a multiplicity of housekeeping information. There is also a field for operator comments made at any time while data is being collected.

47 OTHER INSTRUMENTATION↗
DOE OSTI2015

Ensemble simulations of the role of the stratosphere in the attribution of northern extratropical tropospheric ozone variability

Despite the need to understand the impact of changes in emissions and climate on tropospheric ozone, the attribution of tropospheric interannual ozone variability to specific processes has proven difficult. Here, we analyze the stratospheric contribution to tropospheric ozone variability and trends from 1953 to 2005 in the Northern Hemisphere (NH) mid-latitudes using four ensemble simulations of the free running (FR) Whole Atmosphere Community Climate Model (WACCM). The simulations are externally forced with observed time-varying (1) sea-surface temperatures (SSTs), (2) greenhouse gases (GHGs), (3) ozone depleting substances (ODS), (4) quasi-biennial oscillation (QBO), (5) solar variability (SV) and (6) stratospheric sulfate surface area density (SAD). A detailed representation of stratospheric chemistry is simulated, including the ozone loss due to volcanic eruptions and polar stratospheric clouds. In the troposphere, ozone production is represented by CH 4 –NO x smog chemistry, where surface chemical emissions remain interannually constant. Despite the simplicity of its tropospheric chemistry, at many NH measurement locations, the interannual ozone variability in the FR WACCM simulations is significantly correlated with the measured interannual variability. This suggests the importance of the external forcing applied in these simulations in driving interannual ozone variability. The variability and trend in the simulated 1953–2005 tropospheric ozone from 30 to 90° N at background surface measurement sites, 500 hPa measurement sites and in the area average are largely explained on interannual timescales by changes in the 30–90° N area averaged flux of ozone across the 100 hPa surface and changes in tropospheric methane concentrations. The average sensitivity of tropospheric ozone to methane (percent change in ozone to a percent change in methane) from 30 to 90° N is 0.17 at 500 hPa and 0.21 at the surface; the average sensitivity of tropospheric ozone to the 100 hPa ozone flux (percent change in ozone to a percent change in the ozone flux) from 30 to 90° N is 0.19 at 500 hPa and 0.11 at the surface. The 30–90° N simulated downward residual velocity at 100 hPa increased by 15% between 1953 and 2005. Yet, the impact of this on the 30–90° N 100 hPa ozone flux is modulated by the long-term changes in stratospheric ozone. The ozone flux decreases from 1965 to 1990 due to stratospheric ozone depletion, but increases again by approximately 7% from 1990 to 2005. The first empirical orthogonal function of interannual ozone variability explains from 40% (at the surface) to over 80% (at 150 hPa) of the simulated ozone interannual variability from 30 to 90° N. This identified mode of ozone variability shows strong stratosphere–troposphere coupling, demonstrating the importance of the stratosphere in an attribution of tropospheric ozone variability. The simulations, with no change in emissions, capture almost 50% of the measured ozone change during the 1990s at a variety of locations. This indicates that a large portion of the measured change is not due to changes in emissions, but can be traced to changes in large-scale modes of ozone variability. This emphasizes the difficulty in the attribution of ozone changes, and the importance of natural variability in understanding the trends and variability of ozone. We find little relation between the El Niño–Southern Oscillation (ENSO) index and large-scale tropospheric ozone variability over the long-term record.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2020

Chemical changes in thirdhand smoke associated with remediation using an ozone generator

Ozonation is a common remediation approach to eliminate odors from mold, tobacco and fire damage in buildings. Little information exists to: 1) assess its effectiveness; 2) provide guidance on operation conditions; and 3) identify potential risks associated with the presence of indoor ozone and ozonation byproducts. The goal of this study is to evaluate chemical changes in thirdhand smoke (THS) aerosols induced by high levels of ozone, in comparison with THS aerosols aged under similar conditions in the absence of ozone. Samples representing different stages of smoke aging in the absence of ozone, including freshly emitted secondhand smoke (SHS) and THS, were collected inside an 18-m 3 room-sized chamber over a period of 42 h after six cigarettes were consumed. The experiments involved collection and analysis of gas phase species including volatile organic compounds (VOCs), volatile carbonyls, semivolatile organic compounds (SVOCs), and particulate matter. VOC analysis was carried out by gas chromatography/mass spectrometry with a thermal desorption inlet (TD-GC/MS), and volatile carbonyls were analyzed by on-line derivatization with dinitrophenylhydrazine (DNPH), followed by liquid chromatography with UV/VIS detection. SVOCs were extracted from XAD-coated denuders and Teflon-coated fiberglass filters in the absence of ozone. In those extracts, tobacco-specific nitrosamines (TSNAs) and other SVOCs were analyzed by gas chromatography with positive chemical ionization-triple quadrupole mass spectrometric detection (GC/PCI-QQQ-MS), and polycyclic aromatic hydrocarbons (PAHs) were quantified by gas chromatography with ion trap mass spectrometric detection (GC/IT-MS) in selected ion monitoring mode. Particulate matter concentration was determined gravimetrically. In a second experiment, a 300 mg h -1 commercial ozone generator was operated during 1 h, one day after smoke was generated, to evaluate the remediation of THS by ozonation. VOCs and volatile carbonyls were analyzed before and after ozonation. Extracts from fabrics that were exposed in the chamber before and after ozonation as surrogates for indoor furnishings were analyzed by GC/IT-MS, and aerosol size distribution was studied with a scanning mobility particle sizer. Ozone concentration was measured with a photometric detector. An estimated 175 mg ozone reacted with THS after 1 h of treatment, corresponding to 58% of the total O 3 released during that period. Fabric-bound nicotine was depleted after ozonation, and the surface concentration of PAHs adsorbed to fabric specimens decreased by an order of magnitude due to reaction with ozone, reaching pre-smoking levels. These results suggest that ozonation has the potential to remove harmful THS chemicals from indoor surfaces. However, gas phase concentrations of volatile carbonyls, including formaldehyde, acetaldehyde and acetone were higher immediately after ozonation. Ultrafine particles (UFP, in most cases with size <60 nm) were a major ozonation byproduct. UFP number concentrations peaked shortly after ozonation ended, and remained at higher-than background levels for several hours. Based on these results, minimum re-entry times after ozone treatment were predicted for different indoor scenarios. Clearly defining re-entry times can serve as a practical measure to prevent acute exposures to ozone and harmful ozonation byproducts after treatment. This study evaluated potential benefits and risks associated with THS remediation using ozone, providing insights into this technology.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗